Condensation of hydrocarbons



June 17, 194:7.- `W, A, SMiTH l 2,422,443

CONDENSATION OF HYDROCARBONS Filed Jly 15, 1942 Patented June 17, 1947 f UNITED STATES lPMIeN"T 422,46 roo'NnENsA'rroN oF nxnonnoivs William aivh smith, r'ittsbuilii; ra. pplication July' 145,1 1942', serial lT. 1 olilii. (el. isti-viii This invention relates to the chemical condensation of mineral hydrocarbons of relatively small complexity into hydrocarbons of relatively greater complexity, and isin the nature of an lm provement uponmy prior copending application Serial No.y 426,602, filed January 13, 1942, no vv U. S. Patent No. 2,356,952 granted August 29, 1944,

In my said prorapplicatiom I have disclosed an improved method and apparatus for treating petroleum oils, particularly crude oils,.to increase the percentage of light bodied lubricants by controlledconversion. However, certain crude oils,- such as Cali-forniacrude oils, contain relatively large amounts otlight bodied lubricating components, but are deficient in heavy bodied components, such as are deemed desirable, for example, in the lubrication of aircraft enginesand it is frequently desirable to treat petroleum hydrocarbons of relatively small complexity, particularly light bodied lubricants and the lighter fractions distilled off inthe treatment of crude oils, in order to condensesuch hydrocarbons into heavier bodiedhydroca'rbons, such as those of greater complexity. l, l

A n object of t is invention isto provide an improved method, andv apparatusfor changing mineral hydrocarbons, particularly petroleum, of` relatively small complexity into hydrocarbons ofv greater complexity, which will berelatively simple, practical, inexpensive, and rapid, which will require a minimum of apparatus, and which Will utilize apparatus that is relatively simple and inexpensive.

Another object vof the invention iste provide an improved method and apparatus for condensing mineral hydrocarbons of thepetroleum type into hydrocarbons of greater complexity, which will produce hydrocarbons of the desired com plexity of a high quality and at a relatively low cost. Y Other objects nand advantages Will be apparent from the following description of some em-- bodiments of the invention, and the novel fea-V tures willbe lparticularly pointed out hereinafter in connection with the appended claim.

In the accompanying drawings:l

Fig. l is a diagram illustrating schematically an elevation of asmpleform of apparatus which may be employed in the practice of this inven- Fig. 2 is another elevation illustrating dia--4 grammaticallyaI simple form of apparatus'for use in the chemical condensation of the hydrocarr bonsnot yi r 1.1iquiq;1 form at ordinary room temperatures and pressures.`

i above` approximately b t l Chemiealicndensation .0f retiens.. @ilimitada-ie well understood in. .the industry andrmig' he brieiiy :designated asfthe. opreste er. @liver cracking when applied to petroleum hydroc emaawrewih i drocarbons, Whilejna ,taining such hydrocarbons' in,ilnanateeontct fer a testa dei agnes af time lvvith a, condensation agent',` such ais'. acid'-` activated clay and heat activated bauxite, and prior tothe completion of this'contact, halogenat'- ing the ltl'yiclro'ca-rboris.'I After the. chemical eendencat iomthecond'ens'd hydro ab s aresepar d frornthe condensation agent 1 suitable marinerl.. erretraitly, Vthe halogen accordplishedprior to thel coftactbetvvee c'ndHfl sanoriagent and die hydrcaftts, but not ne." essa'ruly'. *l -1 'w Specific examples of this invention will' ivv be described: ,l As oneexample, a c crude `oil, is'vrst halogen in lflyls'uitable manner, ,as-,fr example,- by" passingffhy'g. dragen .chloride ,eastfleufhih Q11. ridr grer' temperature eonditions, during which ,a consid-i erable amount .ofl tllev gas .is absorlofed't theli'll This fhelogenated. material' is #Hee frix h, nely divided, eikactiveieslslr f h'atl, Cif: vated bauxite,. in which preferablyisalso mi a metallic compound', s uh as cuprous-oxi e, This mixture is thenheatedimany ,suitablel manner, suchasbyj'pumping it through a pipe still', irf which they mixtureis; heated" to a .tern-:1 peratureabove approximately 400 F. andi below that which would cause'. degradation of the hydro'lbs". The' resulting, Chemically Gl'- densednpart is.then;Saperaie 1fr 1n1 Jihacatalysts or condensation agent ,in @rentable-mnner.. hydrocarbqn afe'vatnzediat the smutrniiiefa passedover ardplysi'oally condensed into fcoiiii 3 mon receiver and then later separated into the desired fractional components.

The portion of the oil, after such treatment, which passes off with the condensation agent may then be separated from such agent, such as by filtering, and the agent revivied and re-used. While the hydrocarbonsto be treated are, in this example, halogenated or mixed with the hydrogen chloride gas before being mixed with the condensation agent, it will bel understood that the halogenating medium may be admitted to the hydrocarbons at any point in the treatment prior to completion thereof. Better results appear to be obtained when the halogenation occurs before the mixture with the condensation-agent, or at least early in the heat treatment of the hydrocarbons with the condensation agent. This gives an increase in the heavier oils, and is really a synthesis of the heavier oils, rather than cracking.

When one desires' to chemically condense mineral hydrocarbons that are too volatile to be handledY Y as a liquid in the treatment, these volatile hydrocarbons are halogenated as such under the proper temperature conditions and subjectedat the same time, or subsequently, to con-a densation by bringing them during halogenation or subsequently thereto into intimate or prolonged contact with the condensation agent, such asin pellet form. During the treatment with the condensation agent, the hydrocarbons are heated to a temperature above 400 F., but less than the temperatures which would cause degradation of the hydrocarbons or prevent chemical condensation, and thenafter the hydrocarbons are chemically condensed, they may be physically condensed into liquids and separated, eitherbyk condensing them separately from the condensation agent, or by filtering the same after the agent is added, or in any other suitable manner.

As another example of the invention, the hydrocarbons may be brought into intimate contact withthe condensation agent and a metallic chlorideor an available halogen in the presence of heat, as vexplained in the other two examples above, and the halogen in the form of hydrogen halide appears to Ybe liberated from the metallic compound so as to perform the -halogenation of the hydrocarbons during the reaction in the presence of condensation agents.

Any' suitable condensation agent may be employed, but preferably I employ a product containing aluminum, such as acid-activated clay Orheat-activated' bauxite, as the condensation agent. I have also found that better results are usually obtained, if one incorporates in the acidactivated clay or the heat-activated bauxite, an additional finely divided metallic compound, .such as, for example, various compounds of iron, copper, aluminum, zinc and nickel.

The condensation action is also sometimes improved if the halogenatedhydrocarbon.is brought into contact with the condensation agent while mixed with some other unhalogenated substance, such as benzol, or other hydrocarbons. action is illustrated by the following equation:

I have found that the best results were obtained when the condensation agent had intermixed therewith a cuprous oxide (CuzO) although good results Were obtained with cupric oxideY ('CuO), and with iron sulfate and oxides.V When the halogenation is to occur during the treatment with the condensation agent, I have found that excellent results are obtained by using copper and iron chlorides intermixed with the condensation agent, and the cuprous chlorides appear to be superior to the cupric chlorides. W'hen using the copper chloride with theacid-activated clay, for example, the clay appeared to permit the copper chloride to evolve chlorine in the form of hydrogen chloride, with some halogenation of the organic material. Clay is an impure aluminum silicate containing impurities including iron, and bauxite is a form of aluminum hydroxide, rather impure and also containing iron. Bauxite is activated usually by heat to about 1000o F. The metallic impurities in bauxite and clay, of which ir-ony is a prominent example, appear to aid in the condensation reaction, but such action is in some instances apparently expedited Such an by the addition to the .clay or -bauxite of the other finely divided metallic compounds, such as thosehereinbefore mentioned.

The make-up of the condensation catalyst or agent will depend to some extentupon the nature of .the'materials to belcondens'ed, but as a general rule, the acid-activated clay and heat-activated Ybauxite are each preferably used with the metal compound. "I'he metal compound s usually in the form of an oxide if a reactive atom, such as chlorine, existsv on the materials tov be contacted, but if the lmaterials to be contacted contain double bondsY or somesimilar condition, the desirable component, such as metallic chlorides or other metallic halogens, may be incorporated with the metal, if so desired. Y Y l The condensation agent employed with either o these examples, after use, may be revivied by any of the usual methods known in the industry, and by properly adjusting the various components, continuousoperation and regeneration'is feasible with a minimum expenditure of reagent and utilities. VWith this invention, the large amount of cracked gases obtained from cracking processes may be converted into superior automotive fuels,`Y

or even heavier products, or both.Uv

400 F. and 680 F., nearer the latter, as measuredl with the thermometer bulb immersed in the mixture. It is believed that the actual temperature,V

atthe heating surface may be a little higher because in the application of theprocess by means of a pipe still, the transfer line temperatures to secure similar results may be about higher. The temperature to be used is readily determined experimentally for a given desired reaction, but if the temperature is tooY high, it causes degradation of the materials by cracking, and thus interferes with the condensation.

Referring now to the, drawings, the apparatus shown in Fig. 1 is intended to be diagrammatic and illustrates the principle of the invention when a pipe still is employed. In this apparatus, the mixture of loil and the finely dividedfcondensation agent is Vsupplied .through the reservoir II). This mixture is withdrawn therefrom by 'pipe I I, controlled by valve-l2, lthrough the action of a pump I3. The pumpV I3 delivers the mixture under Apressure throughv the-pipe I4 into oneend of a coil I5 which is disposed in a heating chamber IE. The other end of the coil is yconnected by aY pipe I1, controlled by valve Ila, toga reaction-or flash chamber-i8 having, if desired, a plurality of fractionating chambersY I, 2 3 and 4.

through a heating chamber I9.

hydrocarbons A pipe 2U controlled by a valve 2| opens out of the bottom of the chamber I8, so as to remove the condensation agent and the heavier hydrocarbon components, and this removed mixture is separately treated, such as by filtration, toseparate the condensation agent from theAv liquid medium in which it is carried and which represents the heavier hydrocarbons. .The chambers I5 and i9 are heated in any suitable manner, such as by passing hot gases into the lower end of the chamber I6 through conduit 22 and removing them at the upper end through a pipe 23 controlled by a valve 24. The chamber i9 may be heated by passing hot gases into the same through a flue or pipe 25 controlled by a valve 26, and removing such hot gases from the bottom of the chamber i9 vby a flue 2l controlled by a Valve 28. The chambers l5 and I9 may advantageously be provided in a common casing in which the chambers are separated by a partition 29 having an opening 35 therein adjacent the up-per end thereof, and this opening 35 may be closed or opened to any desired extent, such as by a slide valve 3l. Y

The pipe Il has a branch I'b before its connection to the valve ll'a, which branch after passing through a valve 32 subdivides into a plurality of pipes 33, 34, and 35, controlled respectively by valves 3S, 31 and 38, leading to the upper ends of the fractionating chambers i, 2 and 3. The pipe lib also has a branch pipe 3i) which is connected to a pipe 4Q that leads from the upper end of the top ractionating chamber 4 to the upper end of a physical condensation coil 4 I. The lower end of the coil 4| is connected by a pipe 42 to a reservoir 43 which receives the condensation products. The coil 4| is disposed in a casing 44, and a cooling medium enters the chamber of the casing 44 through an inlet pipe 45 at the bottom, and is removed through an outlet pipe 46 adjacent the top of the casing 44. The fractionating chambers 2, 3 and 4 may have overflow pipes A, B and Cr respectively, which lead to separate cooling devices 4l', 48 and 4Q respectively. This fractionating tower may have any desired number of chambers and may be otherwise constructed in accordance with the usual practice in the oil industry.

If the liquid hydrocarbon to be condensed in this manner is not previously halogenated, the halogen is added to the mixture either in the receptacle l5, or in the pipe I4 by a pipe 53 controlled by valve 5i. If desired, Water or a readily vaporizable hydrocarbon, such as gasoline, may also be added to pipe I4 alone or with the halogen through the pipe 55. Steam or gasoline, or even a halogen gas may also be added through a pipe 5 I a to the lower end of the reaction or flash chamber i8. The outlet from the upper end of the chamber 4 to the pipe 40 may also be provided with a valve 53 at a point below the connection between pipes 39 and 45. By suitable manipulation of the valves, the condensation may be carried on and part of the overhead separated by fractionation into different componentsv through the outlet pipes A, B and C, or all of the overhead may be carried over by the pipe 40 and condensed in the coil lll. This combination overhead is then treated subsequently in any suitable manner to separate off individually the different fractions.

In Fig. 2, a simple form of apparatus is illustrated for handling mineral hydrocarbons in vapor form, which are to be condensed, and in this example, a steel tube 55 is disposed in asvending 0r upright positonandcerineotcd at its upper end to an intake mined@ byivhih. the ,live drocarbons inl vapor ferm are :admitted :under pressure .to the upper endof the tube 55. The tube is lled with the condensation agent or catalyst in pellet for-m, this column of pellets restins upon ons 0.1 more apertured plates 5l in the tube. The lower end of'the tube 55 is connected by a tube conduit 5i t9 e 'receiver 59, but the tube 58 passes through the chamber of a condenser ljll. For this purPOQ 'the tube 53 $1.4?? rounded by a liquid-tight ,tesine and 9991s medium ,is circulated, throng. ihiscasrie @rear-id tube `it s@ as t9 Lili-1.1i@ Pers .elly 20mila-isc the vapors in the tube 58. The physically and chemically condensed hydrocarbons are then discharged through the lower end of the tube 58 into the receiver 59.

The tube 55 is surrounded, along its length, with a plurality of separate heating chambers 5l, 62 and 63 and these chambers may be heated in any suitable manner, such as, for example, by electric heaters with a thermostatic temperature control, so as to selectively control the temperature throughout the whole length of the tube 55. The hydrocarbons to be condensed enter the top of the tube 55 and during their descent through the tube 55, they pass in prolonged contact with the condensation agent. The chemically condensed material is also physically condensed during its descent or in the tube 58. I have found that five or six pounds per square inch pressure on the ingoing vapors is usually sufficient. It will also be understood that liquid hydrocarbons to be condensed chemically may also be passed downwardly through the tube 55 in the same manner as the gases, and they also will be chemically condensed in a similar manner to that of the vaporous hydrocarbons.

Where the hydrocarbons to be treated are rst halogenated, the condensation agent or catalyst may be one free of a halogen, such as the acidactivated clay or the heat-activated bauxite in finely divided but solid form, such as in pellets. Where the hydrocarbons are not first halogenated, the metallic chlorides are incorporated either in the pellets containing the agent, or in separate pellets intermixed with the pellets containing the condensation agent, or otherwise distributed along the path of the hydrocarbons, so that the hydrocarbons in passing through the apparatus will be subjected to the action of the halogen as well as the condensing agent. The metallic compound when used will be incorporated in the pellets, or in separate pellets intermixed with the pellets of the condensation agent.

It will be understood that various changes in the details, materials and arrangements of parts, and in the different steps, which have been herein described and illustrated in order to explain the nature of the invention may be made by those skilled in the art within the principle and scope of the invention, as expressed in the appended claim.

I claim as my invention:

The improved method of chemically condensing petroleum hydrocarbons of relatively small complexity into hydrocarbons of relatively greater complexity which comprises treating said hydrocarbons of small complexity with hydrogenv chloride gas, bringing the treated hydrocarbon into contact, at approximately the same time and for a substantial interval, with acid-activated clay and an oxide of copper, and while at a temperature above approximately 400 F. and below that Vwhich --wuld lcaus vdegradation of the hydrocarbons, and separating the chemically condensed product-from the clay andcopper oxide.

' WILLIAM ALVAH SMITH.,

UNTTED STATES PATENTS Y P ier etal. Y Sept. 13, 1938 Number 8 Name Y .y Date Fenske et al. Oct. 4,1938 Pier et :11.1.y Feb. 13, 1940 Subkow May 21, 1940 Steien Sept. 1, 1942 Gayer Jan. 19,1937 Morrell Dec. 8, 1936 Goldsby et a1 July 13, 1943 Pier et a1 Oct. 24, 1939 Schmerling et a1. Sept. 21, 1943 Hull et al. Apr. 9, 1940 Schmerlng et a1. May 9,1944

Schmerling et al. Dec. 12, 1944 

